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Herein, we report the first mechanochemical strategy for the Ru-catalyzed deoxygenative borylation of free phenols via C-O bond cleavage. This Ru-catalyzed phenolic borylation approach has been successfully extended to the Suzuki-Miyaura-type cross-coupling of phenols with aryl bromides. The protocol accepts a wide scope of phenolic substrates, allowing the synthesis of aryl pinacolboranes and biphenyl structures in excellent yields and serving as a better alternative to classical cross-coupling reactions in the context of pot, atom, and step economy synthesis.
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http://dx.doi.org/10.3390/molecules30081835 | DOI Listing |
Org Lett
September 2025
Shanghai Institute for Advanced Immunochemical Studies & School of Life Science and Technology, ShanghaiTech University, Shanghai 201210, China.
To address the current limitations of DNA-compatible Sonogashira cross-coupling reactions capable of accommodating a broad range of commercially available phenolic building blocks (BBs), an SuFEx-Sonogashira cross-coupling protocol has been developed. This protocol involves the conversion of readily accessible phenolic compounds into the corresponding aryl fluorosulfates within 96-well microplates via a highly efficient liquid-phase SuFEx reaction, followed by Sonogashira cross-coupling with DNA-conjugated terminal alkynes.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Department of Chemistry and Biochemistry, The University of Texas at Dallas, Richardson, Texas 75080-3021, United States.
The direct transformation of C-H bonds into C-C bonds via cross-dehydrogenative coupling (CDC) represents a powerful strategy in synthetic chemistry, enabling streamlined bond construction without the need for prefunctionalized substrates. While traditional CDC approaches rely on polar mechanisms and preactivation of one of the C-H partners, recent advances have introduced radical-based strategies that employ a hydrogen atom transfer (HAT) approach to access carbon-centered radicals from unactivated substrates. Herein, we report a nickel-catalyzed CDC reaction between aldehydes and alkenes for the synthesis of skipped enones, leveraging aryl radicals as intermolecular HAT agents.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China.
The direct cross-coupling of unactivated alkyl halides with aryl or heteroaryl partners remains a fundamental challenge in synthetic chemistry due to their inertness and propensity for side reactions. Herein, we report a transition-metal-free electrochemical halogen-atom transfer strategy that enables efficient alkyl radical cross-coupling via convergent paired electrolysis. In this system, anodically generated α-aminoalkyl radicals mediate the activation of alkyl iodides, while aryl/heteroaryl aldehydes or nitriles undergo cathodic reduction to afford persistent ketyl radical anions or aryl radical anions.
View Article and Find Full Text PDFOrg Lett
September 2025
School of Molecular Sciences, The University of Western Australia, Crawley, WA 6009, Australia.
We report the synthesis of three nickel complexes based on Ni(NHC)[P(OR)](Ar)Cl and their application in C()-N cross-coupling reactions. Reactions involving secondary amines proceeded at room temperature, while anilines and primary alkyl amines coupled under mild heating. The reported complexes are air-stable as solids, operate at low catalytic loading, and do not require an exogenous ligand.
View Article and Find Full Text PDFJ Org Chem
September 2025
Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, New York 14627, United States.
This report presents the alkynyl -Prins cyclization of Achmatowicz adducts, enabling the synthesis of up to 24 (24) highly functionalized [4.3.1] and [3.
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